2성분계 {1,2-dichloropropane+2-(2-methoxyethoxy)ethanol 및 + 2-(2-ethoxyethoxy)ethanol}에 대한 298.15 K에서의 과잉몰엔탈피 및 과잉몰부피

김재원; 김문갑; Jaewon Kim; Moongab Kim

Korean Chemical Engineering Research, Vol.44, No.5, 444-452, October, 2006

Excess Molar Enthalpies and Excess Molar Volumes for the Binary Mixtures {1,2-dichloropropane+2-(2-methoxyethoxy)ethanol, and +2-(2-ethoxyethoxy)ethanol} at 298.15 K

김재원, 김문갑^†

국립상주대학교 응용화학공학부, 742-711 경북 상주시 가장동 386

Jaewon Kim, and Moongab Kim^†

School of Applied Chemical Engineering, Sangju National University, 386, Gajang-dong, Sangju 742-711, Korea

E-mail:

초록

298.15 K 및 1 atm에서 2성분계 {1,2-dichloropropane+2-(2-methoxyethoxy)ethanol} 및 {1,2-dichloropropane+2-(2- ethoxyethoxy)ethanol}에 대한 과잉몰부피와 과잉몰엔탈피를 측정하였다. 과잉몰부피를 측정하기 위한 밀도는 vibrating glass-tube 방식의 densimeter를 이용하였고, 과잉몰엔탈피는 flow mixing 형의 isothermal microcalorimeter를 이용하였다. 측정한 과잉몰부피 및 과잉몰엔탈피는 조성과 상관지어 모두 S자형을 나타내었다. 초기 2-(2-alkoxyethoxy)ethanol 의 강한 자체 회합현상으로 음의 편차를 나타내며, 할로겐화탄화수소 분자의 증가에 따라 2-(2-alkoxyethoxy)ethanol 분자간의 수소결합을 끊기 위한 에너지가 상대적 더 많이 필요함을 보여주고 있다. 실험으로부터 얻어진 V^E_m 및 H^E_m data는 Nelder-Mead의 simplex pattern search method를 이용하여 Redlich-Kister 다항식에 접합(fitting)하였고, Wilson, NRTL 및 UNIQUAC model을 이용하여 data와 H^E_m 조성과의 상관관계를 조사하였다.

This paper reports experimental excess molar volumes V^E_m using a digital vibrating-tube densimeter and excess molar enthalpies H^E_m by means of an isothermal microcalorimeter with a flow mixing cell for the binary mixtures {1,2-dichloropropane + 2-(2-methoxyethoxy)ethanol} and {1,2-dichloropropane + 2-(2-ethoxyethoxy)ethanol} at 298.15 K under atmospheric pressure. All the V^E_m and H^E_m of the two binary mixtures showed S-shaped forms, being negative for poor and positive for rich 1,2-dichloropropane mole fractions. These show that the excess properties were shown to be negative deviation from ideality due to the strong self-association effect among 2-(2-alkoxyethoxy)ethanol molecules at an early stage of mixing, a relatively high energy then is needed to break hydrogen bonds of 2-(2-alkoxyethoxy)ethanol with an increase ofhalogenated hydrocarbon molecular at high mole fraction of 1,2-dichloropropane. The values of excess molar properties(V^E_m and H^E_m) were fitted by the Redlich-Kister equation using Nelder-Mead's simplex pattern search method. The Wilson, NRTL, and UNIQUAC models were used to correlate the H^E_m values.

Keywords:Excess Molar Volumes;Densimeter;Excess Molar Enthalpies;Isothermal Microcalorimeter;1,2-Dichloropropane, 2-(2-methoxyethoxy)ethanol;2-(2-ethoxyethoxy)ethanol;Hydrogen Bond;Redlich-Kister Equation;Wilson;NRTL;UNIQUAC Model

[References]

http://daeyoungchemi.co.kr
Banos I, Valero J, Perez P, Gracia M, Gutierrez L, J. Chem. Thermodyn., 22, 431 (1990)
Barbes B, Garcia I, Gonzalez JA, Cobos JC, Casanova C, Thermochim. Acta, 257, 103 (1995)
Tamura K, Osaki A, Murakami S, Ohji H, Ogawa H, Laurent B, Grolier JPE, Fluid Phase Equilib., 156(1-2), 137 (1999)
Pal A, Singh W, J. Chem. Thermodyn., 28(7), 717 (1996)
Park SJ, Gmehling J, Korean J. Chem. Eng., 12(2), 152 (1995)
Bae HK, Song HC, Korean J. Chem. Eng., 15(6), 615 (1998)
Park SB, Kim JS, Lee H, J. Chem. Thermodyn., 31(10), 1265 (1999)
Kim MG, Lee YS, J. Kor. Soc. of Ind., 4, 193 (2001)
Kim MG, Lee YS, Kim YW, “Excess Molar Volumes and Excess Molar Enthalpies for {1,2-dichloropropane + 2-ethoxyethanol} at T=298.15 K,” Proceedings of 2001 KIChE Fall Meeting, 7(2), 3619-3622 (2001)
Kim MG, Lee YS, “Excess Molar Enthalpies for {1,2- dichloropropane + 2-alkoxyethanol} at T=298.15 K,” Proceedings of 2002 KIChE Spring Meeting, 8(1), 849-852 (2002)
Kim Y, Kim M, Korean Chem. Eng. Res., 42(4), 426 (2004)
Kim JW, “Excess Molar Volumes and Excess Molar Enthalpies for Binary Mixtures of {1,2-dichloropropane + 2-(2-methoxyethoxy) ethanol, and + 2-(2-ethoxyethoxy)ethanol} at 298.15 K,” M. S. Dissertation, Sangju National University, Sangju, Korea (2005)
Redlich O, Kister AT, Ind. Eng. Chem., 40, 345 (1948)
Nelder JA, Mead R, Comput. J., 7, 308 (1965)
Wilson GM, J. Am. Chem. Soc., 86, 127 (1964)
Renon H, Prausnitz JM, AIChE J., 14, 135 (1968)
Abrams DS, Prausnitz JM, AIChE J., 21, 116 (1975)
Riddick JA, Bunger WS, Sakano TK, Organic Solvents, Physical Properties and Methods of Purification, 4th ed., Wiley Interscience Publication, New York (1986)
Sabbah R, An XW, Chickos JS, Leitao MLP, Roux MV, Torres LA, Thermochim. Acta, 331(2), 93 (1999)
Wadso I, Thermochim. Acta, 347(1-2), 73 (2000)
Tanaka R, D’arcy PJ, Benson GC, Thermochim. Acta, 11, 163 (1975)
Chand A, Fenby DB, J. Chem. Thermodyn., 10, 997 (1978)
Costigan MJ, Hodges LJ, Marsh KN, Stokes RH, Tuxford CW, Aust. J. Chem., 33, 2103 (1980)
Prausnitz JM, Lichtenthaler RN, de Azevedo EG, Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd ed., Prentice-Hall, New Jersey (1999)

[Referenced By]

[1] http://daeyoungchemi.co.kr

[2] Banos I, Valero J, Perez P, Gracia M, Gutierrez L, J. Chem. Thermodyn., 22, 431 (1990)

[3] Barbes B, Garcia I, Gonzalez JA, Cobos JC, Casanova C, Thermochim. Acta, 257, 103 (1995)

[4] Tamura K, Osaki A, Murakami S, Ohji H, Ogawa H, Laurent B, Grolier JPE, Fluid Phase Equilib., 156(1-2), 137 (1999)

[5] Pal A, Singh W, J. Chem. Thermodyn., 28(7), 717 (1996)

[6] Park SJ, Gmehling J, Korean J. Chem. Eng., 12(2), 152 (1995)

[7] Bae HK, Song HC, Korean J. Chem. Eng., 15(6), 615 (1998)

[8] Park SB, Kim JS, Lee H, J. Chem. Thermodyn., 31(10), 1265 (1999)

[9] Kim MG, Lee YS, J. Kor. Soc. of Ind., 4, 193 (2001)

[10] Kim MG, Lee YS, Kim YW, “Excess Molar Volumes and Excess Molar Enthalpies for {1,2-dichloropropane + 2-ethoxyethanol} at T=298.15 K,” Proceedings of 2001 KIChE Fall Meeting, 7(2), 3619-3622 (2001)

[11] Kim MG, Lee YS, “Excess Molar Enthalpies for {1,2- dichloropropane + 2-alkoxyethanol} at T=298.15 K,” Proceedings of 2002 KIChE Spring Meeting, 8(1), 849-852 (2002)

[12] Kim Y, Kim M, Korean Chem. Eng. Res., 42(4), 426 (2004)

[13] Kim JW, “Excess Molar Volumes and Excess Molar Enthalpies for Binary Mixtures of {1,2-dichloropropane + 2-(2-methoxyethoxy) ethanol, and + 2-(2-ethoxyethoxy)ethanol} at 298.15 K,” M. S. Dissertation, Sangju National University, Sangju, Korea (2005)

[14] Redlich O, Kister AT, Ind. Eng. Chem., 40, 345 (1948)

[15] Nelder JA, Mead R, Comput. J., 7, 308 (1965)

[16] Wilson GM, J. Am. Chem. Soc., 86, 127 (1964)

[17] Renon H, Prausnitz JM, AIChE J., 14, 135 (1968)

[18] Abrams DS, Prausnitz JM, AIChE J., 21, 116 (1975)

[19] Riddick JA, Bunger WS, Sakano TK, Organic Solvents, Physical Properties and Methods of Purification, 4th ed., Wiley Interscience Publication, New York (1986)

[20] Sabbah R, An XW, Chickos JS, Leitao MLP, Roux MV, Torres LA, Thermochim. Acta, 331(2), 93 (1999)

[21] Wadso I, Thermochim. Acta, 347(1-2), 73 (2000)

[22] Tanaka R, D’arcy PJ, Benson GC, Thermochim. Acta, 11, 163 (1975)

[23] Chand A, Fenby DB, J. Chem. Thermodyn., 10, 997 (1978)

[24] Costigan MJ, Hodges LJ, Marsh KN, Stokes RH, Tuxford CW, Aust. J. Chem., 33, 2103 (1980)

[25] Prausnitz JM, Lichtenthaler RN, de Azevedo EG, Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd ed., Prentice-Hall, New Jersey (1999)